Crystalline transition metal oxy-hydroxide molybdate

ABSTRACT

A hydroprocessing catalyst has been developed. The catalyst is a unique crystalline transition metal oxy-hydroxide molybdate material. The hydroprocessing using the crystalline ammonia transition metal oxy-hydroxide molybdate material may include hydrodenitrification, hydrodesulfurization, hydrodemetallation, hydrodesilication, hydrodearomatization, hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority from Provisional Application No.62/267,862 filed Dec. 15, 2015, the contents of which are herebyincorporated by reference.

FIELD OF THE INVENTION

This invention relates to a new hydroprocessing catalyst. Moreparticularly this invention relates to a unique crystalline transitionmetal oxy-hydroxide molybdate and its use as a hydroprocessing catalyst.The hydroprocessing may include hydrodenitrification,hydrodesulfurization, hydrodemetallation, hydrodesilication,hydrodearomatization, hydroisomerization, hydrotreating, hydrofining,and hydrocracking.

BACKGROUND

In order to meet the growing demand for petroleum products there isgreater utilization of sour crudes, which when combined with tighterenvironmental legislation regarding the concentration of nitrogen andsulfur within fuel, leads to accentuated refining problems. The removalof sulfur (hydrodesulfurization—HDS) and nitrogen(hydrodenitrification—HDN) containing compounds from fuel feed stocks istargeted during the hydrotreating steps of refining and is achieved bythe conversion of organic nitrogen and sulfur to ammonia and hydrogensulfide respectively.

Since the late 1940s the use of catalysts containing nickel (Ni) andmolybdenum (Mo) or tungsten (W) have demonstrated up to 80% sulfurremoval. See for example, V. N. Ipatieff, G. S. Monroe, R. E. Schaad,Division of Petroleum Chemistry, 115^(th) Meeting ACS, San Francisco,1949. For several decades now there has been an intense interestdirected towards the development of materials to catalyze the deepdesulfurization, in order to reduce the sulfur concentration to the ppmlevel. Some recent breakthroughs have focused on the development andapplication of more active and stable catalysts targeting the productionof feeds for ultra low sulfur fuels. Several studies have demonstratedimproved HDS and HDN activities through elimination of the support suchas, for example, Al₂O₃. Using bulk unsupported materials provides aroute to increase the active phase loading in the reactor as well asproviding alternative chemistry to target these catalysts.

More recent research in this area has focused on the ultra deepdesulfurization properties achieved by a Ni-Mo/W unsupported‘trimetallic’ material reported in, for example, U.S. Pat. No.6,156,695. The controlled synthesis of a broadly amorphous mixed metaloxide consisting of molybdenum, tungsten and nickel, significantlyoutperformed conventional hydrotreating catalysts. The structuralchemistry of the tri-metallic mixed metal oxide material was likened tothe hydrotalcite family of materials, referring to literature articlesdetailing the synthesis and characterization of a layered nickelmolybdate material, stating that the partial substitution of molybdenumwith tungsten leads to the production of a broadly amorphous phasewhich, upon decomposition by sulfidation, gives rise to superiorhydrotreating activities.

The chemistry of these layered hydrotalcite-like materials was firstreported by H. Pezerat, contribution à l'étude des molybdates hydratesde zinc, cobalt et nickel, C. R. Acad. Sci., 261, 5490, who identified aseries of phases having ideal formulas MMoO₄.H₂O, EHM₂O⁻(MoO₄)₂.H₂O, andE_(2-x)(H₃O)_(x)M₂O(MoO₄)₂ where E can be NH₄ ⁺, Na⁺ or K⁺ and M can beZn²⁺, Co²⁺ or Ni²⁺.

Pezerat assigned the different phases he observed as being Φc, Φy or Φyand determined the crystal structures for Φx and Φy, however owing to acombination of the small crystallite size, limited crystallographiccapabilities and complex nature of the material, there were doubtsraised as to the quality of the structural assessment of the materials.During the mid 1970 s, Clearfield et al attempted a more detailedanalysis of the Φx and Φy phases, see examples A. Clearfield, M. J.Sims, R. Gopal, Inorg. Chem., 15, 335; A. Clearfield, R. Gopal, C. H.Saldarriaga-Molina, Inorg. Chem., 16, 628. Single crystal studies on theproduct from a hydrothermal approach allowed confirmation of the Φxstructure, however they failed in their attempts to synthesize Φy andinstead synthesized an alternative phase, Na—Cu(OH)(MoO₄), see A.Clearfield, A. Moini, P. R. Rudolf, Inorg. Chem., 24, 4606.

The structure of Φy was not confirmed until 1996 when by Ying et al.Their investigation into a room temperature chimie douce synthesistechnique in the pursuit of a layered ammonium zinc molybdate led to ametastable aluminum-substituted zincite phase, prepared by thecalcination of Zn/Al layered double hydroxide (Zn₄Al₂(OH)₁₂CO₃.zH₂O).See example D. Levin, S. L. Soled, J. Y. Ying, Inorg. Chem., 1996, 35,4191-4197. This material was reacted with a solution of ammoniumheptamolybdate at room temperature to produce a highly crystallinecompound, the structure of which could not be determined throughconventional ab-initio methods. The material was indexed, yieldingcrystallographic parameters which were the same as that of an ammoniumnickel molybdate, reported by Astier, see example M. P. Astier, G. Dji,S. Teichner, J. Ann. Chim. (Paris), 1987, 12, 337, a material belongingto a family of ammonium-amine-nickel-molybdenum oxides closely relatedto Pezerat's materials. Astier did not publish any detailed structuraldata on this family of materials, leading to Ying et al reproducing thematerial to be analyzed by high resolution powder diffraction in orderto elucidate the structure. Ying et al named this class of materials‘layered transition-metal molybdates’ or LTMs.

SUMMARY OF THE INVENTION

A unique crystalline transition metal oxy-hydroxide molybdate materialhas been produced and optionally sulfided, to yield an activehydroprocessing catalyst. The crystalline transition metal oxy-hydroxidemolybdate material has a unique x-ray powder diffraction pattern showingstrong peaks at 9.65, 7.3 and 5.17 Å. The crystalline transition metaloxy-hydroxide molybdate material has the formula:(NH₄)_(a)M(OH)_(b)Mo_(x)O_(y)where “a” varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0;‘M’ is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixturesthereof; ‘b’ varies from 0.1 to 2; ‘x’ varies from 0.5 to 1.5, or from0.75 to 1.5, or from 0.8 to 1.2; ‘y’ is a number which satisfies the sumof the valency of a, M, b and x; the material having a unique x-raypowder diffraction pattern showing peaks at the d-spacings listed inTable A:

TABLE A d (Å) I/I₀ % 10.0-9.53 m 7.72-7.76 s 7.49-7.25 m 5.27-5.12 m 5.1-5.04 m 4.92-4.87 w 3.97-3.92 m 3.69-3.64 s 3.52-3.48 m 3.35-3.32 m3.31-3.29 m 3.12-3.09 w   3-2.97 m 2.76-2.73 m

Another embodiment involves a method of making a crystalline transitionmetal oxy-hydroxide molybdate material having the formula:(NH₄)_(a)M(OH)_(b)Mo_(x)O_(y)where “a” varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0;‘M’ is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixturesthereof; ‘b’ varies from 0.1 to 2; ‘x’ varies from 0.5 to 1.5, or from0.75 to 1.5, or from 0.8 to 1.2; ‘y’ is a number which satisfies the sumof the valency of a, M, b and x; the material having a unique x-raypowder diffraction pattern showing peaks at the d-spacings listed inTable A:

TABLE A d (Å) I/I₀ % 10.0-9.53 m 7.72-7.76 s 7.49-7.25 m 5.27-5.12 m 5.1-5.04 m 4.92-4.87 w 3.97-3.92 m 3.69-3.64 s 3.52-3.48 m 3.35-3.32 m3.31-3.29 m 3.12-3.09 w   3-2.97 m 2.76-2.73 m

The method comprising forming a reaction mixture containing NH₃, H₂O,and sources of M and Mo; adjusting the pH of the reaction mixture to apH of from about 8.5 to about 10; reacting the mixture together atelevated temperature with an autogenous pressure and then recovering thecrystalline transition metal oxy-hydroxide molybdate material.

Yet another embodiment involves a conversion process comprisingcontacting a feed with a catalyst at conversion conditions to give atleast one product, the catalyst comprising: a crystalline transitionmetal oxy-hydroxide molybdate material having the formula:(NH₄)_(a)M(OH)_(b)Mo_(x)O_(y)where “a” varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0;‘M’ is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixturesthereof; ‘b’ varies from 0.1 to 2; ‘x’ varies from 0.5 to 1.5, or from0.75 to 1.5, or from 0.8 to 1.2; ‘y’ is a number which satisfies the sumof the valency of a, M, b and x; the material having a unique x-raypowder diffraction pattern showing peaks at the d-spacings listed inTable A:

TABLE A d (Å) I/I₀ % 10.0-9.53 m 7.72-7.76 s 7.49-7.25 m 5.27-5.12 m 5.1-5.04 m 4.92-4.87 w 3.97-3.92 m 3.69-3.64 s 3.52-3.48 m 3.35-3.32 m3.31-3.29 m 3.12-3.09 w   3-2.97 m 2.76-2.73 m

Additional features and advantages of the invention will be apparentfrom the description of the invention, the FIGURE and claims providedherein.

BRIEF DESCRIPTION OF THE DRAWING

The FIGURE is the x-ray powder diffraction pattern of a crystallinebis-ammonia metal oxy-hydroxide molybdate prepared by boilingcrystallization as described in Examples 1 to 3.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a crystalline transition metaloxy-hydroxide molybdate composition and a process for preparing thecomposition. The material has the designation UPM-8. This compositionhas an empirical formula:(NH₄)_(a)M(OH)_(b)Mo_(x)O_(y)where “a” varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0;‘M’ is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixturesthereof; ‘b’ varies from 0.1 to 2; ‘x’ varies from 0.5 to 1.5, or from0.75 to 1.5, or from 0.8 to 1.2; ‘y’ is a number which satisfies the sumof the valency of a, M, b and x.

The crystalline composition of the invention is characterized by havingan extended network of M-O-M, where M represents a metal, or combinationof metals listed above. The structural units repeat itself into at leasttwo adjacent unit cells without termination of the bonding. Thecomposition can have a one-dimensional network, such as, for example,linear chains.

The crystalline transition metal oxy-hydroxide molybdate compositionhaving a unique x-ray powder diffraction pattern showing peaks at thed-spacings listed in Table A.

TABLE A d (Å) I/I₀ % 10.0-9.53 m 7.72-7.76 s 7.49-7.25 m 5.27-5.12 m 5.1-5.04 m 4.92-4.87 w 3.97-3.92 m 3.69-3.64 s 3.52-3.48 m 3.35-3.32 m3.31-3.29 m 3.12-3.09 w   3-2.97 m 2.76-2.73 m

The crystalline transition metal oxy-hydroxide molybdate composition ofthe invention having the x-ray powder diffraction pattern shown in theFIGURE.

The crystalline transition metal oxy-hydroxide molybdate composition isprepared by solvothermal crystallization of a reaction mixture typicallyprepared by mixing reactive sources of molybdenum with the appropriatemetal ‘M’ with a solvent as well as a source of ammonia. Specificexamples of the molybdenum source which may be utilized in thisinvention include but are not limited to molybdenum trioxide, ammoniumdimolybdate, ammonium thiomolybdate, and ammonium heptamolybdate.Sources of other metals “M” include but are not limited to therespective halide, acetate, nitrate, carbonate, thiols and hydroxidesalts. Specific examples include nickel chloride, cobalt chloride,nickel bromide, cobalt bromide, magnesium chloride, nickel nitrate,cobalt nitrate, iron nitrate, manganese nitrate, zinc nitrate, nickelacetate, cobalt acetate, iron acetate, nickel carbonate, cobaltcarbonate, zinc carbonate, nickel hydroxide and cobalt hydroxide.

The source of ammonia may include but is not limited to ammoniumhydroxide, ammonium carbonate, ammonium bicarbonate, ammonium chloride,ammonium fluoride or a combination thereof.

Generally, the solvothermal process used to prepare the composition ofthis invention involves forming a reaction mixture wherein all of thecomponents, such as for example, Ni, Mo, NH₃ and H₂O are mixed insolution together. By way of specific examples, a reaction mixture maybe formed which in terms of molar ratios of the oxides is expressed bythe formula:AMO_(x):BMoO_(y):C(NH₃):H₂Owhere ‘M’ is selected from the group consisting of iron, cobalt, nickel,manganese, copper, zinc and mixtures thereof; ‘A’ represents the molarratio of ‘M’ and varies from 0.1 to 3 or from 0.5 to 2 or from 0.75 to1.25; ‘x’ is a number which satisfies the valency of ‘M’; ‘B’ representsthe molar ratio of ‘Mo’ and varies from 0.1 to 3 or from 0.5 to 2 orfrom 0.75 to 1.25; ‘y’ is a number satisfies the valency of ‘Mo’; ‘C’represents the molar ratio of NH₃ and varies from 0.01 to 50 or from 0.1to 40 or from 1 to 30 ; the molar ratio of H₂O and varies from 10 to1000 or from 50 to 500 or from 90 to 300. The pH of the mixture isadjusted to a value ranging from about 8.5 to about 10. The pH of themixture is adjusted to a value ranging from about 7.5 to about 11, orfrom about 8.5 to about 10. The pH of the mixture can be controlledthrough the addition of a base such as NH₄OH, quaternary ammoniumhydroxides, amines, and the like.

Once the reaction mixture is formed, the reaction mixture is reacted attemperatures ranging from about 100° C. to about 230° C. for a period oftime ranging from 30 minutes to around 14 days. In one embodiment thetemperate range for the reaction is from about 115° C. to about 125° C.and in another embodiment the temperature is in the range of from about180° C. to about 200° C. In one embodiment, the reaction time is fromabout 4 to about 6 hours, and in another embodiment the reaction time isfrom about 4 to 7 days. The reaction is carried out under atmosphericpressure or in a sealed vessel under autogenous pressure. In oneembodiment the synthesis may be conducted in an open vessel under refluxconditions. The crystalline transition metal oxy-hydroxide molybdatecompositions are recovered as the reaction product. The crystallinetransition metal oxy-hydroxide molybdate compositions are characterizedby their unique x-ray powder diffraction pattern as shown in Table Aabove and the FIGURE.

Once formed, the crystalline transition metal oxy-hydroxide molybdatecomposition may have a binder incorporated, where the selection ofbinder includes but is not limited to, anionic and cationic clays suchas hydrotalcites, pyroaurite-sjogrenite-hydrotalcites, montmorilloniteand related clays, kaolin, sepiolites, silicas, alumina such as (pseudo)boehomite, gibbsite, flash calcined gibbsite, eta-alumina, zicronica,titania, alumina coated titania, silica-alumina, silica coated alumina,alumina coated silicas and mixtures thereof, or other materialsgenerally known as particle binders in order to maintain particleintegrity. These binders may be applied with or without peptization. Thebinder may be added to the bulk crystalline transition metaloxy-hydroxide molybdate composition, and the amount of binder may rangefrom about 1 to about 30 wt % of the finished catalysts or from about 5to about 26 wt% of the finished catalyst. The binder may be chemicallybound to the crystalline transition metal oxy-hydroxide molybdatecomposition, or may be present in a physical mixture with thecrystalline transition metal oxy-hydroxide molybdate composition.

The crystalline transition metal oxy-hydroxide molybdate composition,with or without an incorporated binder can then be sulfided orpre-sulfided under a variety of sulfidation conditions, these includethrough contact of the crystalline transition metal oxy-hydroxidemolybdate composition with a sulfur containing feed as well as the useof a gaseous mixture of H₂S/H₂. The sulfidation of the crystallinetransition metal oxy-hydroxide molybdate composition is performed atelevated temperatures, typically ranging from 50 to 600° C., or from 150to 500° C., or from 250 to 450° C.

The unsupported crystalline transition metal oxy-hydroxide molybdatematerial of this invention can be used as a catalyst or catalyst supportin various hydrocarbon conversion processes. Hydroprocessing processesis one class of hydrocarbon conversion processes in which thecrystalline transition metal oxy-hydroxide molybdate material is usefulas a catalyst. Examples of specific hydroprocessing processes are wellknown in the art and include hydrodenitrification, hydrodesulfurization,hydrodemetallation, hydrodesilication, hydrodearomatization,hydroisomerization, hydrotreating, hydrofining, and hydrocracking.

The operating conditions of the hydroprocessing processes listed abovetypically include reaction pressures from about 2.5 MPa to about 17.2MPa, or in the range of about 5.5 to about 17.2 MPa, with reactiontemperatures in the range of about 245° C. to about 440° C., or in therange of about 285° C. to about 425° C. Time with which the feed is incontact with the active catalyst, referred to as liquid hour spacevelocities (LHSV), should be in the range of about 0.1 h⁻¹ to about 10h⁻¹, or about 2.0 h⁻¹ to about 8.0 h⁻¹. Specific subsets of these rangesmay be employed depending upon the feedstock being used. For examplewhen hydrotreating a typical diesel feedstock, operating conditions mayinclude from about 3.5 MPa to about 8.6 MPa, from about 315° C. to about410° C., from about 0.25/h to about 5/h, and from about 84 Nm³ H₂/m³ toabout 850 Nm³ H₂/m³ feed. Other feedstocks may include gasoline,naphtha, kerosene, gas oils, distillates, and reformate.

Examples are provided below so that the invention may be described morecompletely. These examples are only by way of illustration and shouldnot be interpreted as a limitation of the broad scope of the invention,which is set forth in the appended claims.

Patterns presented in the following examples were obtained usingstandard x-ray powder diffraction techniques. The radiation source was ahigh-intensity, x-ray tube operated at 45 kV and 35 mA. The diffractionpattern from the copper K-alpha radiation was obtained by appropriatecomputer based techniques. Powder samples were pressed flat into a plateand continuously scanned from 3° and 70° (2θ). Interplanar spacings (d)in Angstrom units were obtained from the position of the diffractionpeaks expressed as θ, where θ is the Bragg angle as observed fromdigitized data. Intensities were determined from the integrated area ofdiffraction peaks after subtracting background, “I_(o)” being theintensity of the strongest line or peak, and “I” being the intensity ofeach of the other peaks. As will be understood by those skilled in theart the determination of the parameter 2θ is subject to both human andmechanical error, which in combination can impose an uncertainty ofabout ±0.4° on each reported value of 2θ. This uncertainty is alsotranslated to the reported values of the d-spacings, which arecalculated from the 2θ values. In some of the x-ray patterns reported,the relative intensities of the d-spacings are indicated by thenotations vs, s, m, and w, which represent very strong, strong, medium,and weak, respectively. In terms of 100(I/I₀), the above designationsare defined as:

-   -   w=0-15, m=15-60: s=60-80 and vs=80-100.

In certain instances the purity of a synthesized product may be assessedwith reference to its x-ray powder diffraction pattern. Thus, forexample, if a sample is stated to be pure, it is intended only that thex-ray pattern of the sample is free of lines attributable to crystallineimpurities, not that there are no amorphous materials present. As willbe understood to those skilled in the art, it is possible for differentpoorly crystalline materials to yield peaks at the same position. If amaterial is composed of multiple poorly crystalline materials, then thepeak positions observed individually for each poorly crystallinematerials would be observed in the resulting summed diffraction pattern.Likewise it is possible to have some peaks appear at the same positionswithin different, single phase, crystalline materials, which may besimply a reflection of a similar distance within the materials and notthat the materials possess the same structure.

EXAMPLE 1

In a 2 liter flask, 116.4 g of nickel nitrate hexahydrate (0.4 moles ofNi) and 70.58 g of ammonium heptamolybdate (0.4 moles of Mo) weredissolved in 720 ml of water. To this solution, concentrated NH₄OH (˜30ml) was added until the pH reached around 9. At this point the solutionwas transferred to a 2-liter stainless steel autoclave, the heat wasramped to 150° C. over a period of 2 hours and held at 150° C. for 7days, after which time the autoclave was cooled to room temperature,filtered, washed with 90 ml of about 90° C. water and then dried at 100°C. The x-ray powder diffraction spectra of the phase matches the spectrashown in the FIGURE.

EXAMPLE 2

In a 2 liter flask, 58.2 g of nickel nitrate hexahydrate (0.2 moles ofNi) and 35.29 g of ammonium heptamolybdate (0.2 moles of Mo) weredissolved in 360 ml of water. To this solution, concentrated NH₄OH (˜25ml) was added until the pH reached around 9. At this point the solutionwas transferred to a 2-liter stainless steel autoclave, the heat wasramped to 200° C. over a period of 2 hours and held at 200° C. for 3hours, after which time the autoclave was cooled to room temperature,filtered, washed with 90 ml of about 90° C. water and then dried at 100°C. The x-ray powder diffraction spectra of the phase matches the spectrashown in the FIGURE.

EXAMPLE 3

In a 2 liter flask, 58.2 g of cobalt nitrate hexahydrate (0.2 moles ofNi) and 35.29g of ammonium heptamolybdate (0.2 moles of Mo) weredissolved in 360 ml of water. To this solution, concentrated NH₄OH (˜25ml) was added until the pH reached around 9. At this point the solutionwas transferred to a 2-liter stainless steel autoclave, the heat wasramped to 200° C. over a period of 2 hours and held at 200° C. for 5days, after which time the autoclave was cooled to room temperature,filtered, washed with 90 ml of about 90° C. water and then dried at 100°C. The x-ray powder diffraction spectra of the phase matches the spectrashown in the FIGURE.

EMBODIMENTS

Embodiment 1 is a crystalline transition metal oxy-hydroxide molybdatematerial having the formula:(NH₄)_(a)M(OH)_(b)Mo_(x)O_(y)where “a” varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0;‘M’ is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixturesthereof; ‘b’ varies from 0.1 to 2; ‘x’ varies from 0.5 to 1.5, or from0.75 to 1.5, or from 0.8 to 1.2; ‘y’ is a number which satisfies the sumof the valency of a, M, b and x; the material having a unique x-raypowder diffraction pattern showing peaks at the d-spacings listed inTable A:

TABLE A d (Å) I/I₀ % 10.0-9.53 m 7.72-7.76 s 7.49-7.25 m 5.27-5.12 m 5.1-5.04 m 4.92-4.87 w 3.97-3.92 m 3.69-3.64 s 3.52-3.48 m 3.35-3.32 m3.31-3.29 m 3.12-3.09 w   3-2.97 m 2.76-2.73 m

The crystalline transition metal oxy-hydroxide molybdate material ofembodiment 1 wherein the crystalline transition metal oxy-hydroxidemolybdate material is present in a mixture with at least one binder andwherein the mixture comprises up to 25 wt % binder.

The crystalline transition metal oxy-hydroxide molybdate material ofembodiment 1 wherein the crystalline transition metal oxy-hydroxidemolybdate material is present in a mixture with at least one binder andwherein the mixture comprises up to 25 wt % binder and wherein thebinder is selected from the group consisting of silicas, aluminas, andsilica-aluminas.

The crystalline transition metal oxy-hydroxide molybdate material ofembodiment 1 wherein M is nickel or cobalt.

The crystalline transition metal oxy-hydroxide molybdate material ofembodiment 1 wherein M is nickel.

The crystalline transition metal oxy-hydroxide molybdate material ofembodiment 1 wherein the crystalline transition metal oxy-hydroxidemolybdate material is sulfided.

Embodiment 2 is a method of making a crystalline transition metaloxy-hydroxide molybdate material having the formula:(NH₄)_(a)M(OH)_(b)Mo_(x)O_(y)where “a” varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0;‘M’ is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixturesthereof; ‘b’ varies from 0.1 to 2; ‘x’ varies from 0.5 to 1.5, or from0.75 to 1.5, or from 0.8 to 1.2; ‘y’ is a number which satisfies the sumof the valency of a, M, b and x; the material having a unique x-raypowder diffraction pattern showing peaks at the d-spacings listed inTable A:

TABLE A d (Å) I/I₀ % 10.0-9.53 m 7.72-7.76 s 7.49-7.25 m 5.27-5.12 m 5.1-5.04 m 4.92-4.87 w 3.97-3.92 m 3.69-3.64 s 3.52-3.48 m 3.35-3.32 m3.31-3.29 m 3.12-3.09 w   3-2.97 m 2.76-2.73 m

the method comprising: (a) forming a reaction mixture containing H₂O,and sources of NH₃, M and Mo; (b) adjusting the pH of the reactionmixture to a pH of from about 8.5 to about 10; (c) reacting the reactionmixture between 100 and 220° C. in an autogenous environment; and (d)recovering the crystalline transition metal oxy-hydroxide molybdatematerial.

The method of embodiment 2 wherein the reacting is conducted at atemperature of from 100° C. to about 200° C. for a period of time fromabout 30 minutes to 14 days.

The method of embodiment 2 wherein the recovering is by filtration orcentrifugation.

The method of embodiment 2 further comprising adding a binder to therecovered crystalline transition metal oxy-hydroxide molybdate material.

The method of embodiment 2 further comprising adding a binder to therecovered crystalline transition metal oxy-hydroxide molybdate materialwherein the binder is selected from the group consisting of aluminas,silicas, and alumina-silicas.

The method of embodiment 2 further comprising sulfiding the recoveredcrystalline transition metal oxy-hydroxide molybdate material.

Embodiment 3 is a conversion process comprising contacting a feed with acatalyst at conversion conditions to give at least one product, thecatalyst comprising: a crystalline transition metal oxy-hydroxidemolybdate material having the formula:(NH₄)_(a)M(OH)_(b)Mo_(x)O_(y)where “a” varies from 0.1 to 10, or from 0.5 to 5, or from 0.75 to 2.0;‘M’ is a metal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixturesthereof; ‘b’ varies from 0.1 to 2; ‘x’ varies from 0.5 to 1.5, or from0.75 to 1.5, or from 0.8 to 1.2; ‘y’ is a number which satisfies the sumof the valency of a, M, b and x; the material having a unique x-raypowder diffraction pattern showing peaks at the d-spacings listed inTable A:

TABLE A d (Å) I/I₀ % 10.0-9.53 m 7.72-7.76 s 7.49-7.25 m 5.27-5.12 m 5.1-5.04 m 4.92-4.87 w 3.97-3.92 m 3.69-3.64 s 3.52-3.48 m 3.35-3.32 m3.31-3.29 m 3.12-3.09 w   3-2.97 m 2.76-2.73 m

The process of embodiment 3 wherein the conversion process ishydroprocessing.

The process of embodiment 3 wherein the conversion process is selectedfrom the group consisting of hydrodenitrification, hydrodesulfurization,hydrodemetallation, hydrodesilication, hydrodearomatization,hydroisomerization, hydrotreating, hydrofining, and hydrocracking

The process of embodiment 3 wherein the crystalline transition metaloxy-hydroxide molybdate material is present in a mixture with at leastone binder and wherein the mixture comprises up to 25 wt % binder.

The process of embodiment 3 wherein the crystalline transition metaloxy-hydroxide molybdate material is sulfided.

The invention claimed is:
 1. A crystalline transition metaloxy-hydroxide molybdate material having the formula:(NH₄)_(a)M(OH)_(b)Mo_(x)O_(y) where ‘a’ varies from 0.1 to 10; ‘M’ is ametal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; ‘b’ranges from 0.1 to 2; ‘x’ ranges from 0.5 to 1.5; and ‘y’ is a numberwhich satisfies the sum of the valences of a, M, b and x; the materialhaving a x-ray powder diffraction pattern showing peaks at thed-spacings listed in Table A: TABLE A d (Å) I/I₀ % 10.0-9.53 m 7.72-7.76s 7.49-7.25 m 5.27-5.12 m  5.1-5.04 m 4.92-4.87 w 3.97-3.92 m 3.69-3.64s 3.52-3.48 m 3.35-3.32 m 3.31-3.29 m 3.12-3.09 w   3-2.97 m 2.76-2.73 m


2. The crystalline transition metal oxy-hydroxide molybdate material ofclaim 1 wherein the crystalline transition metal oxy-hydroxide molybdatematerial is present in a mixture with at least one binder and whereinthe mixture comprises up to 25 wt % binder.
 3. The crystallinetransition metal oxy-hydroxide molybdate material of claim 2 wherein thebinder is selected from the group consisting of silicas, aluminas, andsilica-aluminas.
 4. The crystalline transition metal oxy-hydroxidemolybdate material of claim 1 wherein M is nickel or cobalt.
 5. Thecrystalline transition metal oxy-hydroxide molybdate material of claim 1wherein M is nickel.
 6. The crystalline transition metal oxy-hydroxidemolybdate material of claim 1 wherein the crystalline transition metaloxy-hydroxide molybdate material is sulfided.
 7. A method of making acrystalline transition metal oxy-hydroxide molybdate material having theformula:(NH₄)_(a)M(OH)_(b)Mo_(x)O_(y) where ‘a’ varies from 0.1 to 10; ‘M’ is ametal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; ‘b’ranges from 0.1 to 2; ‘x’ ranges from 0.5 to 1.5; and ‘y’ is a numberwhich satisfies the sum of the valences of a, M, b and x; the materialhaving a x-ray powder diffraction pattern showing peaks at thed-spacings listed in Table A: TABLE A d (Å) I/I₀ % 10.0-9.53 m 7.72-7.76s 7.49-7.25 m 5.27-5.12 m  5.1-5.04 m 4.92-4.87 w 3.97-3.92 m 3.69-3.64s 3.52-3.48 m 3.35-3.32 m 3.31-3.29 m 3.12-3.09 w   3-2.97 m 2.76-2.73 m.

the method comprising: (a) forming a reaction mixture containing NH₃,H₂O, and sources of M and Mo; (b) adjusting the pH of the reactionmixture to a pH of from about 8.5 to about 10; (c) reacting the reactionmixture between about 100 and about 220° C. in an autogenousenvironment; and (d) recovering the crystalline transition metaloxy-hydroxide molybdate material.
 8. The method of claim 7 wherein thereacting is conducted at a temperature of from 100° C. to about 200° C.for a period of time from about 30 minutes to 14 days.
 9. The method ofclaim 7 wherein the recovering is by filtration or centrifugation. 10.The method of claim 7 further comprising adding a binder to therecovered crystalline transition metal oxy-hydroxide molybdate material.11. The method of claim 10 wherein the binder is selected from the groupconsisting of aluminas, silicas, and alumina-silicas.
 12. The method ofclaim 7 further comprising sulfiding the recovered crystallinetransition metal oxy-hydroxide molybdate material.
 13. A hydroprocessingconversion process comprising contacting a feed with a catalyst athydroprocessing conditions to give at least one product, the catalystcomprising: a crystalline transition metal oxy-hydroxide molybdatematerial having the formula:(NH₄)_(a)M(OH)_(b)Mo_(x)O_(y) where ‘a’ varies from 0.1 to 10; ‘M’ is ametal selected from Mg, Mn, Fe, Co Ni, Cu, Zn and mixtures thereof; ‘b’ranges from 0.1 to 2; ‘x’ ranges from 0.5 to 1.5; and ‘y’ is a numberwhich satisfies the sum of the valences of a, M, b and x; the materialhaving a x-ray powder diffraction pattern showing peaks at thed-spacings listed in Table A: TABLE A d (Å) I/I₀ % 10.0-9.53 m 7.72-7.76s 7.49-7.25 m 5.27-5.12 m  5.1-5.04 m 4.92-4.87 w 3.97-3.92 m 3.69-3.64s 3.52-3.48 m 3.35-3.32 m 3.31-3.29 m 3.12-3.09 w   3-2.97 m 2.76-2.73 m.


14. The process of claim 13 wherein the conversion process is selectedfrom the group consisting of hydrodenitrification, hydrodesulfurization,hydrodemetallation, hydrodesilication, hydrodearomatization,hydroisomerization, hydrotreating, hydrofining, and hydrocracking. 15.The process of claim 13 wherein the crystalline transition metaloxy-hydroxide molybdate material is present in a mixture with at leastone binder and wherein the mixture comprises up to 25 wt % binder. 16.The process of claim 13 wherein the crystalline transition metaloxy-hydroxide molybdate material is sulfide.